Composition and process for treating cellulose containing textile material



United States Patent 3 035,942 COMPOSITION AND PROCESS FOR TREATING CELLULOSE CONTAINING TEXTILE MATERIAL Theodore F. Cooke, Martinsville, and Philip B. Roth, Somerville, N.J., assignors to American Cyanamid Company, New York, N.Y., a corporation of Maine No Drawing. Filed July 15, 1958, Ser. No. 748,593 8 Claims. (Cl. 117-139.4)

The present invention relates to novel water-soluble textile finishing compositions, to the process for applying them to textile materials, and to the textile materials so treated.

More particularly, the present invention relates to novel water-soluble textile finishing compositions, comprising a novel mixture of heretofore described textile finishing resins, the combination of which and their use on textile materials results in unexpected advantage, insofar as certain properties of the finished textile materials are concerned.

The formaldehyde or methylol condensates, and more particularly, the dimethylol condensates of tetrahydro-S- alkyl-s-triazinone textile resins have been described as finishes for cellulosic textile materials for purposes of imparting wrinkle recovery to the materials, and more particularly, the treated fabric. When resins of this class are applied to cellulosic textile materials, the finished material may generally be described as being somewhat inferior with respect to the measure of wrinkle recovery after laundering, as well as with respect to the tensile strength of the finished fabric after laundering when compared wtih similar material finished wtih melamine resins. Further, cotton fabrics treated with this class of resins tend to discolor when ironed after laundering. However, the triazinones, as a class of resins, are less expensive than the melamine resins, and when they are subjected to repeated laundering in which chlorine bleach is employed,

are not as subject to discoloration as white fabrics finished with melamine resins.

It is an object of the present invention to provide a textile finishing compositoin containing melamine resin and triazinone resins which when applied to cellulose containing textile materials, the finished material is characterized by all the desirable features capable of being imparted by each of the resinous components.

vIt is a further object of the present invention to provide such a composition, which when applied to cellulose containing textile materials results in a surprising and synergistic effect with respect to the wrinkle recovery and tensile strength of said finished materials, which have been subjected to laundering.

These and other objects and advantages of the present invention will become more apparent from the detailed description set forth hereinbelow.

In accordance with the present invention, a composition is provided, comprising a triazinone selected from the group consisting of triazinones of the following general formula:

HO CHPNl and N-di-substituted amino or amido.

where R may be alkyl, aralkyl, hydroxyalkyl, alkoxyalkyl, halogenoalkyl, and dialkylaminoalkyl, and triazinones having the following general formula:

o 0 it t HO CH2N/ \NCH2OH HO CHsN NCHrOH H2O CH2 112G E2 N -R-N II where R is an alkylene group containing from 2 to 6 carbon atoms, substituted by alkyl, aryl, aralkyl, hydroxy, alkoxy, halogen, and dialkylamino, and polymethylol meiamines.

These triazinones may be identified as monoor bismethylolated tetrahydro-s-triazines substituted in the 5- position by a member selected from the group consisting of alkyl, aralkyl, hydroalkyl, alkoxyalkyl, dialkylaminoalkyl, and halogenoalkyl.

The formaldehyde condensates of triazinones within the above-described formulas have been disclosed as textile finishing materials for imparting crease-proofing or wrinkle recovery to cellulose textiles, as for example, in US. Patent 2,321,989, and the triazinones as compounds are described in US. Patents 2,016,521 and 2,304,624. In general, these compounds, and particularly the compounds ofthe class described and defined by general Formula I hereinabove, may be prepared by reacting dimethylol urea with a primary amine. The primary amine, which is aliphatic, may be saturated, branched, or straightchained, or it may be a cyclic, alicyclic, and substituted or not-substituted with inert groups, i.e., groups which do not interfere with the formation of the tetrahydro triazinone, as for example, phenyl, halogeno, hydroxy, alkoxy,

Such amines include, among others, methylamine, ethylamine, tertiary butyl amine, octadecylamine, propylamine, furfurylamine, ethanolamine, 3-methoxypropylamine, dimethylamine, ethylene diamine, tetraethylene diamine, and the like.

In accordance with the present invention, the dimethylol derivatives of the tetrahydro-s-triazines described in general Formula I employable herein may have, for example, one of the following substituents in the 5-position: methyl, ethyl, propyl, tertiary butyl, octadecyl, hexadecyl, Z-hydroxyethyl, 3-methoxypropyl, and the like.

As examples of suitable compounds included by general Formula I, the following are illustrative: 1,3-dimethylol-3,4,5,6-tetrahydro-S-methyl-s-triazin-Z- one; l,3-dimethylol-3,4,5,6tetrahydro-5-ethyl-s-triaz.in-2- one; 1,3-dimethylol-3,4,5,6-tetrahydro-5-octadecyl-s-triaziu- 2-one; l,3-dimethylol-3,4,5,6-tetrahydro-5-(2-hydroxyethyl)- s-triazin-Z-one;

1,3 -dimethylol-3 ,4,5 6-tetrahydro-5- (3-methoxypropyl striazin-2-one;

1,3-dimethylol-3,4,5,6-tetrahydro-5-benzyl-s-triazin-2- one;

1, 3-dimethylol-3 ,4,5,6-tetrahydro-5- (dimethyl aminornetbyl) -s-tri azin-2-one;

l, 3-dimethylol-3 ,4,5 ,6-tetrahydro-5- 2-furyl) -s-.triazin- 2-one;

1},3-dimethylol-3,4,5,6-tetrahydro-5-(3-chloropropyl)- s-triazin-Z-one;

3 1,3 -dimethylol-3,4,5 ,6-tetral1ydro-5 -cyclohexyl-s-triazin- 2-one; 1,3-dimethylol-3,4,5,6-tetrahydro--tert. butyl-s-tn'azin- 2-one; and l,3-dimethylol-3,4,5,6-tetrahydro-5-allyl-s-triazin-Z-one.

As an example of the types shown in Formula II in the general expression of the invention set forth hereinabove, R may be an ethylene radical, in which case the compound is 1,l',3,3-tetramethylol-5,5'-ethylene-bis(tetrahydro-s-triazinone). As examples of suitable compounds included by general Formula. II, the following are illustrative:

l, 1 ,3,3'-tetramethylol-5 ,5 -trimethylene-bis(3,4,5 ,6-

tetrahydro-s-triazin-Z-one) l, l ,3,3'-tetramethylol-5 ,5 -hexamethylene-bis- 3 ,4,5 ,6-

tetrahydro-s-triazin-Z-one) 1, 1 ,3,3'-tetramethylol-5 ,5 l-methyltetramethylene) bis-(3 ,4,5,6-tetrahydro-s-triazine-2-one);

1, 1,3,3'-. tetramethyl0l-5 ,5 1,4-dimethyltetramethylene) -bis- 3 ,4,5 ,6-tetrahydro-s-triazin-2-one) 1, 1 ,3,3'-tetramethylol-5 ,5 1,4-cyclohexylene -bis- (3,4,5 ,6-tetrahydro-s-triazin-Z-one) l, l,3 ,3'-tetramethylol-5 ,5 (Z-chlorotrimethylene) -bis- (3,4,5,6-tetrahydro-s-triazin-Z-one) 1,1 ',3,3"-tetramethylol-5 ,5 (Z-phenyltetramethylene) bis- (3,4,5 ,6-tetrahydro-s-triazin-Z-one) and l, l',3,3tetramethylol-5 ,5- l-methoxyethylene) -bis- (3,4,5 ,6-tetrahydro-s-txiazin-2-one) It will be apparent that a great plurality of other polymethylol tetrahydro triazinones may also be employed, and in addition, their alkylated derivatives, such as those reacted with saturated aliphatic alcohols, as for example, in accordance with the procedure described and outlined in US. Patent 2,321,989.

Thus, in accordance with the present invention, when the expression methylolated tetrahydro-s-triazine and similar expressions are employed herein, it is intended to refer not only to the methylolated or formaldehyde condensates of these materials, but also the lower alkyl alcohol derivatives, including those employing saturated aliphatic alcohols containing from -1 to 4 carbon atoms. Thus, for example, the methylolated tetrahydro-s-triazines may be alkylated with methyl, ethyl, propyl, isopropyl, butyl, and tertiary butyl alcohols, in accordance with the general procedure outlined in the above-referred to patent.

The polymethylolated melamines employable in the present invention are substantially fully etherified, substantially fully methylolated melamines.

In the present specification, by the expression substantially fully methylolated melamine as that and similar expressions are used, it is meant that the melamine component contains a minimum of 5.8 moles of combined formaldehyde per mole of melamine and preferably up to 6 moles of combined formaldehyde per mole of melamine.

By the expression substantially fully etherified as it is employed herein it is meant that substantially all of the available methylol groups (at least 5.6 groups) on the melamine have been reacted with methanol, ethanol or other suitable etherifying' agents. The alcohol employable may be a suitable saturated aliphatic alcohol containing from 1 to 4 carbon atoms, as for example, ethyl, methyl, propyl, isopropyl, butyl and tertiary butyl alcohol, though of these, methyl derivative is greatly preferred, in

. that the reaction product is characterized by better watersolubility and stability characteristics. By way of example, a suitable polymethyl melamine is hexamethyl hexamethylol melamine.

The methylol condensates of the tetrahydro-s-triazines of this invention, including the alkylated derivatives, are characterized by. good stability and ready solubility in water, as is the melamine component in accordance with this invention. Thus, the textile finishing composition of this invention may generally be described as a watersoluble or water-dispersible finishing composition.

With respect to both the triazi-nones and the polymethylol melamines, it should be noted that these materials may be identified or characterized as being essentially monomeric. In this connection, if the material is in part polymerized or contains low order polymeric material, the degree of polymerization is insufiicient to adversely aifect the water-solpbility characteristics of the composition.

The ratio of triazinones and the melamine resins employable in accordance with the invention may be varied within fairly wide limits in accordance with the present invention, and still result in unexpected and surprising a tensile strength and wrinkle recovery for laundered cellulose containing textile materials treated therewith. In general, on a mole basis, the triazinone may be employed with respect to the melamine component in ratios of from 1:10 to 40:1. It will, of course, be appreciated that at these outside limitations, the unexpected effort achieved is considerably less noticeable and advantageous than when these materials are employed within the preferred mole ratios of from 1:4 to 20:1, triazinone to melamine, respectively.

The water-soluble composition for finishing cellulose containing textile materials in accordance with this invention are applied to the material, preferably a cellulosic fabric, from an aqueous solution, normally containing a catalyst or an accelerator to assist in its cure on the fabric. The resin composition of this invention may be applied to the cellulose containing textile material by any conventional finishing techniques, as immersion, padding, spraying, and the like, followed where necessary by squeezing, hydro extraction, or similar processes, in order to aflix the desired amount of resin solids onto the fabric.

The method of application should be such so that from about 1 to 15%, and in some instances, higher amounts of the resin composition based on the dry weight of the fabric are deposited thereon. Within certain limits, the amount of resin applied depends upon the particular type of fabric treated. Thus, when treated fabrics consisting of fibrous cellulosic materials are used, the concentration of the order of from about 1 to 15% and in particular, from 3 to 10% resin solids on the weight of the fabric is employed.

The catalyst or curing accelerator employed, preferably in the aqueous treating, impregnating or finishing composition, may consist of the type comprising free acid, acid salts, alkanolamine salts and the like. The concentration of catalyst employed may range from between about 0.1 to about 25% or higher, based on the weight of resin solids, depending upon the particular catalyst type employed. Thus, for example, from between about 0.1 to about 10% of a free acid, such as phosphoric, oxalic and the like may be employed, while in the case of ammonium chloride, amounts of from between 0.5 and about 10% are used. In the case of amine salts, including alcohol amine salts, from about 1.0 to about 10% are most useful, while with respect to salts such as magnesium chloride, amounts of about 5 to 25% have been successfully employed. In all instances, the concentration of the catalyst is based on the weight of resin solids employed.

Following the application of the resin composition and curing catalyst to the textile fabric, the material is sub- Q temperatures employed and, of course, is influenced by whether or not separate or combined drying and curing steps are employed.

Generally, when drying and curing is carried out in a combined step, a time of from about 1 minute to 10 minutes may be employed at temperatures of from about 450 to 250 F respectively. When the fabric has been dried preliminary to curing, curing times from 5 minutes to A minute at temperatures of 250 to 450 F., respectively, have been successfully employed.

By cellulose containing textile material as it and similar expressions are employed herein, it is meant textile materials containing at least 50% cellulose, such as cotton, regenerated cellulose, such as viscose, linen and the like. Preferably, the textile material is all cellulose, and preferably cotton, though it may be blended with synthetic or natural textile materials, as for example, the nylons, the acrylics, the polyesters, and wool fibers, an the like.

By the term textile material as that and similar terms are employed herein, it is meant filaments, yarns, fibers and fabrics, whether the latter be felted, woven, or non-woven, or otherwise formed.

In order that the present invention may be more fully understood, the following examples are given primarily by way of illustration. No specific details or enumerations contained therein should be construed as limitations on the present invention, except as they appear in the appended claims. All parts and percentages are by Weight.

EXAMPLE 1 (Preparation of Dimethylol Ethyl Triazinone Resin) 120 parts (2.0 moles) of urea and 324 parts (4.0 moles) of 37% aqueous solution of formaldehyde, adjusted to a pH of 8.5 with caustic soda solution, were charged into a suitable reaction vessel and stirred for 30 minutes at 75 C. After gradual cooling to 60 C., the temperature was reduced to 5 C. Thereafter, 128 parts (2.0 moles) of ethylamine was added to the reaction mixture over a 20 minute period, causing the temperature to rise to 41 C. The reaction mixture was then heated to 95 C. for 2 hours and cooled to 70 C. Then 324 parts (4.0 moles) of 37% formaldehyde was added to the reaction mixture, and it was stirred for 30 minutes at 75 C. The final product was obtained by concentrating this reaction mixture in vacuo until 740 parts remained at a pH of 8.7 and a total solids of 64.6.

Stirring was continued for an additional 2 hours while maintaining the temperature at 40 C. and thereafter the pH was adjusted to a value between 8 and 10 with caustic soda. The reaction mixture was then filtered and the filtrate was concentrated under a vacuum of 26 to 28 inches of mercury until the pot temperature reached 80 C. The syrupy product weighed 814 parts and contained 84% solids. It was easily soluble in water in all proportions and was fluid and clear after six months at 25 and 37 C.

EXAMPLE 2 Three pad baths were prepared containing 7.5% resin solids and 12% of magnesium chloride as an accelerator, based on the weight of the resin solids. Pad bath A contained 7.5% of a fully Water-soluble, stable, substantially fully methylated hexamethylol melamine, pad bath B contained 7.5% of the triazinone prepared in accordance with Example 1, and pad bath C contained 7.5% of equal molecular amounts of said hexamethyl hexamethylol melamine and triazinone prepared in accordance with Example 1.

Thereafter, bleached 80 x 80 cotton percale was fed through said baths, so as to apply 6% resin solids therefrom based on the weight of the fabric. The fabrics were dried at 225 F. for 1 minute and cured at 350 F. for 1.5 minutes.

Wrinkle Recovery (Total, degrees): 45 1m Table I hereinbelow shows the actual amounts of resin used in the pad baths.

1 Equimolecular amounts of the two resins (1: 1 mole ratio).

In Table 11 hereinbelow, the values reported and tests referred to were obtained as follows:

Wrinkle recovery was measured on a Monsanto Wrinkle Recovery Tester and the values are reported in degrees, following the tentative test method 66-1956 described on page 158 of the 1957 Technical Manual and Yearbook of the American Association of Textile Chemists and Colorists, volume 33.

The tensile strength was measured on a Scott Tester according to A.S.T.M. standards.

The 160 F. wash under Wrinkle Recovery were carried out by the procedure described under Test Method 36-1957 111 on page 94 of the above reference.

The 212 F. wash under Wrinkle Recovery in Table II were carried out by the procedure described under Test Method 14-1953 on page 123 of the above reference, using a Najort washer.

The 160 F. and 180 F. washes under Tensile Strengthin Table II were carried out by the procedure described as Test Method 13-1953 using temperatures of 160 and 180 F., respectively, with Tide, a synthetic detergent manufactured by Proctor & Gamble in place of soap and with a 0.02% available chlorine in the wash liquor.

In Table II are shown the results of the tests run on the fabric treated as described in Example 2. The headings A, B and C correspond to the headings described in Table I.

TAB LE l'l Untreated A B 0 soda) 162 233 218 231 After 52l2 Washes 146 200 193 202 Tensile Strength (Total, pounds):

Initial 96 57 66 62 After 5160 Washes (Tide Chiorine) 75 55 48 56 After 5180 Wa es (Tide Chlorine) 53 46 27 45 Table II hereinabove clearly illustrates the compositions in accordance with the present invention result in a synergistic effect, both with respect to the tensile strength of cellulosic textile material, and with respect to the Wrinkle recovery of cellulosic textile materials finished therewith. While this synergistic effect is less pronounced with respect to initial tensile strength, it will be noted that it becomes very evident when the material is laundered. It should further be noted that this effect becomes increasingly more pronounced as the severity of the laundering conditions increase.

EXAMPLE 3 A pad bath was prepared containing 7.5% resin solids composed of a triazinone to melamine molar ratio of 3:1 in which the triazinone was tetramethylol-S,5'-ethylenebis-(tetrahydro-s-triazinone) and the melamine component was a substantially fully etherified, substantially fully methylolated melamine. The pad bath contained 12% magnesium chloride as'a curing accelerator, based on the Weight of the resin solids. l i 7' 80 x 80 bleached cotton percale was fed through the above composition, so as to apply 6% resin solids, based accordance with this procedure exhibited a tensile strength H superior to that provided by either of the components of the composition alone when applied in equalsolids amounts on the fabric, namely, 6%, and it was noted that this effect became more increased as laundering conditions for the finished fabric were increased in severity.

EXAMPLE 4 Pad baths were prepared as in Example 2, using blends of the products of Example 1 and a Water-soluble hexamethyl hexamethylol melamine. Applications of 6% total resin solids were made on 80 x 80 cotton percale as in Example 2, and after curing at 350 F. for 1.5 minutes, the treated fabrics were process washed.

Table HI hereinbelow shows the composition of the resin blends in the pad baths.

TAB LE III Percent Molar Ratio Percent Hexamethyl of Melamine Blend Product of hexamethylol Component Example 1 melamine to Productof Example 1 *In Table IV hereinbelow, the values reported were obtained as in Example 2. The headings A, B, C, etc.

When the values found for initial wrinkle, recovery and tensile strength were plotted against the molar ratios of the blends, the points were closely coincident to a straight line drawn between the 100% values for each component. However, when similar plots were made for the values found for wrinkle recovery and tensile strength after washing, the points fell on curves above the straight line drawn between 100% of each compound. This demonstrates that a synergistic 'eifect exists for the blends. Tables V and VI below show the difierences between the values found for wrinkle recovery and tensile strength after washing and the expected values (taken from the straight line curve) on a molar ratio basis.

TABLE VI Tensile Strength After Blend Found .9160 F. Washes Calculated on Molar Basis The composition of this invention may be employed with other textile finishing resins, either thermosetting or thermoplastic, in so long as these other finishing mater-ials do not interfere with or significantly reduce or retard the synergistic elfect achieved with respect to the tensile strength of cellulosic textile materials finished in accordance with this invention. Thus, for example, the composition of this invention may be employed with urea formaldehyde resins, ethylene urea formaldehyde resins, 1,2-propylene urea formaldehyde resins, 1,3-propylene urea formaldehyde resins or their alkylated derivatives. Additionally, phenol formaldehyde resins, ketone-formaldehyde resins, as for example, acetone-formaldehyde resins, epoxy resins, as for example, polyglycidyl ethers of polyhydric alcohols, such as the diglycidyl ethers of ethylene glycol, and the like, may be used. Among thermoplastic resins which may be mentioned are monopolymers or copolymers of acrylates, such as methylacrylate, ethylacrylate, butylacrylate, methylmethacrylate, butylmethacrylate, or copolymers of these or their equivalents with styrene, including ring and chain substituted styrenes, acrylonitrile, polyvinyl chloride, and the like. In addition, the composition of this invention may be employed with softeners, stifieners, lubricants, dicyanamide and other conventional treating bath finishing components.

We claim:

1. An aqueous composition comprising a member selected from the group consisting of monoand bis-methylolated tetrahydro-s-triazines substituted in the 5-position by a member selected from the group consisting of alkyl, aralkyl, hydroalkyl, alkoxyalkyl, dialkylaminoalkyl, and halogenoalkyl, and a substantially fully etherified substantially fully methylolated melamine, wherein the methylolated tetrahydro-s-triazine and melamine component are employed in molecular ratios of from 1:10 to 40: 1, respectively.

2 An aqueous solution comprising a member selected from the group consisting of monoand bisfully methylolated tetrahydro-s-triazine, substituted in the 5-position by a member selected from the group consisting of alkyl, aralkyl, hydroalkyl, alkoxyalkyl, dialkylaminoalkyl, and halogenoalkyl, and a substantially fully etherified substantially fully methylolated melamine, wherein the methylolated tetrahydro-s-triazine and melamine component are employed in molecular ratios of from 1:10 to 40:1, respectively.

' 3. A composition according to claim 2 in which the tetrahydro-s-triazine is dimethylol ethyltriazinone.

4. A composition according to claim 2 in which the tetrahydro-s-triazine and the melamine component are present in molecular ratios of 1:4 to 20:1, respectively.

5. A process for finishing cellulose containing textile materials to impart wrinkle recovery'and shrinkage control thereto, which comprises applying from an aqueous solution a composition containing a member selected from the group consisting of monoand bis-methylolated tetrahydro s-triazine substituted in the 5-position by a member selected from the group consisting of alkyl,

aralkyl, hydroalkyl, alkoxyalkyl, dialkylaminoalkyl, and halogenoalkyl, and a substantially fully etherified substantially fully methylolated melamine, said tetrahydro-striazine and said melamine component being employed 9 in molecular ratios of from 1:10 to 40:1, respectively, and thereafter curing said composition in the presence of an accelerator to a water-insoluble state.

6. A process according to claim 5 in which the textile material is cotton.

7. A cellulose containing textile material characterized by shrinkage control and wrinkle recovery and improved tensile strength, having a heat-cured, water-insoluble product of a mixture comprising a member selected from the group consisting of monoand bis-methylolated tetrahydro-s-triazine substituted in the 5-position by a member selected from the group consisting of alkyl, aralkyl, hydroalkyl, alkoxyalkyl, dialkylaminoalkyl, and halogenoalkyl, and a substantially fully etherified substantially fully metliylolated melamine, said tetrahydro-s-triazine and said melamine being employed in molecular ratios of from 1:10 to 40:1, respectively.

8. A textile material according to claim 7 in which the material is cotton.

References Cited in the file of this patent UNITED STATES PATENTS 2,321,989 Burke June 15, 1943 2,690,404 Spangler et a1 Sept. 28, 1954 2,901,463 Hurwitz Aug. 25, 1959 

5. A PROCESS FOR FINISHING CELLULOSE CONTAINING TEXTILE MATERIALS TO IMPART WRINKLE RECOVERY AND SHRINKAGE CONTROL THERETO, WHICH COMPRISES APPLYING FROM AN AQUEOUS SOLUTION A COMPOSITION CONTAINING A MEMBER SELECTED FROM THE GROUP CONSISTING OF MONO- AND BIS-METHYLOLATED TETRAHYDRO-S-TRIAZINE SUBSTITUTED IN THE 5-POSITION BY A MEMBER SELECTED FROM THE GROUP CONSISTING OF ALKYL, ARALKYL, HYDROALKYL, ALKOXYALKYL, DIALKYLAMINOALKYL, AND HALOGENOALKYL, AND A SUBSTANTIALLY FULLY ETHERIFIED SUBSTANTIALLY FULLY METHYLOLATED MELAMINE, SAID TETRAHYDRO-STRIAZINE AND SAID MELAMINE, COMPONENT BEING EMPLOYED IN MOLECULAR RATIOS OF FROM 1:10 TO 40:1, RESPECTIVELY, AND THEREAFTER CURING SAID COMPOSITION IN THE PRESENCE OF AN ACCELERATOR TO A WATER-INSOLUBLE STATE. 